Patent GB-966860-A (GB)
Title: Organometallic compounds
Inventor: DUBECK MICHAEL
IPC: C07F15/04
Filed: 1960-11-08
Abstract: The invention comprises organo metallic compounds of formula: QC­CQ1.Cy(Ni)xCy1 wherein Q and Q1 are each hydrogen, C1-C10 univalent hydrocarbon radicals, or electron withdrawing groups, Cy and Cy1 are cyclopentadienyl hydrocarbon groups (as defined), x is 1 or 2 and when x is 2 and Q is hydrogen or phenyl, Q1 is an electron withdrawing group. Cy and Cy1 may be the same or different and are hydrocarbon groups of formulae: <FORM:0966860/C1/1> <FORM:0966860/C1/2> wherein the R1s are hydrogen or univalent hydrocarbon radicals, the complete radical preferably containing 5 to 13 carbon atoms. Typical electron withdrawing groups are specified. The above formula includes compounds of formula: QC­CQ1.CyNiNiCy1 of structural formula: <FORM:0966860/C1/3> Suitable univalent hydrocarbon radicals may have polar substituents separated by at least two carbon atoms from the acetylenic bond; thus suitable acetylenic compounds are perhalo butynes, propargyl alcohol, ethynyl cyclohexanol, beta carboxy esters of the butynes, pentynes, hexynes and heptynes and 5-methoxy pentyne-1. Other compounds have the formula: QC­CQ1.CyNiCy1 which may have the structure (in the case of dicyclopentadienyl nickeldimethyl butyndioate) <FORM:0966860/C1/4> These compounds may be hydrogenated at the double bond of the cyclopentadienyl ring attached to the acetylene compound.  Both groups of compounds may be prepared by reacting a compound of formula CyNixCy1 with an acetylenic compound of formula QC­CQ1 where Q,Q1,Cy,Cy1 and x are as above defined. If desired the resulting compound may be treated with ZC­CZ1 where Z and Z1 are electron withdrawing groups. The reaction is carried out between -30 DEG  and 110 DEG C., at a pressure from atmospheric to 10,000 psig (preferably to 250 psig) if desired in the presence of a solvent (which may be the acetylenic compound itself, or an ether, ester or silicone oil) and preferably under an inert blanket of nitrogen, helium or argon. Typical compounds prepared in the examples include bis(cyclopentadienyl nickel) acetylene; (v) bis (cyclopentadienyl nickel) propyne; (vi) bis(cyclopentadienyl nickel) hexyne-3, (x) bis(cyclopentadienyl nickel) phenyl acetylene; (xi) bis (cyclopentadienyl nickel) perfluorobutyne-2, (xiii) bis(cyclopentadienyl nickel) dimethyl acetylene dicarboxylate and (xiv) dicyclopentadienyl nickel-dimethyl-sym-butyndioate.ALSO:Cyclopentadienyl nickel acetylenic compounds of formula QC­CQ1.Cy(Ni)xCy1 wherein Q and Q1 are each hydrogen, univalent C1-10 hydrocarbon radicals or electron withdrawing groups, Cy and Cy1 are cyclopentadienyl or indenyl groups which may be substituted by univalent hydrocarbon radicals, x is 1 or 2 and when x is 2 and Q is hydrogen or a phenyl radical, Q1 is an electron withdrawing group, may be added:  (a) to paints, varnish, printing inks, oil enamels and drying oil synthetic resins to improve their drying characteristics;  (b) as anti-knock agents to liquid hydrocarbon fuels, especially those in the gasoline boiling range.  A specified additive is bis(cyclopentadienyl nickel) hexyne-3.  The base fuel may contain all types of hydrocarbons, paraffins (straight and branched chain), olefins, cycloaliphatics and aromatics. Additionally there may be present an organolead anti-knock agent together with a conventional halohydrocarbon scavenger.  Example XXI describes a gasoline composition containing tetraethyl lead, ethylene dichloride, ethylene dibromide and bis(cyclopentadienyl nickel)pentyne-1.ALSO:Cyclopentadienyl nickel acetylenic compounds of formula QC­CQ1.Cy(Ni)xCy1 wherein Q and Q1 are each hydrogen, univalent C1-10 hydrocarbon radicals or electron withdrawing groups, Cy and Cy1 are cyclopentadienyl or indenyl groups which may be substituted by univalent hydrocarbon radicals, x is 1 or 2 and when x is 2 and Q is hydrogen or a phenyl group Q1 is an electron withdrawing group may be used in gas phase metal plating. They may be thermally decomposed in an atmosphere of a reducing gas such as hydrogen or a neutral atmosphere such as nitrogen to form metallic films on a substrate.